EP1982380B1 - Integrated fuel cell and a production method - Google Patents

Integrated fuel cell and a production method Download PDF

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Publication number
EP1982380B1
EP1982380B1 EP06847219A EP06847219A EP1982380B1 EP 1982380 B1 EP1982380 B1 EP 1982380B1 EP 06847219 A EP06847219 A EP 06847219A EP 06847219 A EP06847219 A EP 06847219A EP 1982380 B1 EP1982380 B1 EP 1982380B1
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EP
European Patent Office
Prior art keywords
layer
fuel cell
channels
thin
recess
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Expired - Fee Related
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EP06847219A
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German (de)
French (fr)
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EP1982380A1 (en
Inventor
Mathieu Roy
Fabien Pierre
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STMicroelectronics SA
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STMicroelectronics SA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1097—Fuel cells applied on a support, e.g. miniature fuel cells deposited on silica supports
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0232—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making
    • Y10T29/49115—Electric battery cell making including coating or impregnating

Definitions

  • the present invention relates to a fuel cell and an integrated fuel cell manufacturing method.
  • the figure 1 represents an example of an integrated fuel cell cell made using microelectronics techniques.
  • This cell is formed on a support plate consisting of a silicon wafer 1 coated with a first insulating thin layer 2 and a second insulating layer 3 thicker.
  • An opening is formed in a portion of the insulating layer 3. In this opening are successively deposited a support layer 4, a catalyst layer 5, an electrolyte layer 6 and a second catalyst layer 7. All of these layers constitutes an active stack 8.
  • An electrode 10, placed on the first insulating layer 2 is in contact with the support layer 4 on the side of the lower face of the cell stack.
  • An opening 11 in the second insulating layer 3 provides access to the electrode 10.
  • An upper electrode 12 is in contact with the upper catalyst layer 7.
  • the electrodes 10 and 12 are provided with openings, and channels 13 are formed in the silicon wafer 1 facing openings in the lower face metallization.
  • the lower and upper electrodes 12 respectively constitute an anode collector and a cathode collector.
  • the electrolyte 6 is, for example, a polymeric acid such as Nafion in solid form and the catalyst layers are, for example, layers based on carbon and platinum. This is only an example of realization.
  • Various types of fuel cells that can be produced in the form illustrated in figure 1 are known in the art.
  • H + protons which are directed towards the electrolyte 6 and, on the other hand, electrons which are directed by the outside of the stack, to the anode collector 10.
  • the H + protons pass through the electrolyte 6 to join the catalyst layer 7 where they recombine with oxygen and electrons arriving from the outside of the cell by the collector cathode.
  • a positive potential is obtained on the cathode collector 12 (oxygen side) and a negative potential on the anode collector 10 (hydrogen side).
  • a disadvantage of this type of fuel cell is the phenomena occurring at the outlet of the channels 13 for introducing hydrogen. It turns out in practice that instead of the reactions occurring over the entire surface of the lower catalyst layer 5, these reactions actually occur only on a part of this surface corresponding substantially to the area occupied by the openings of the hydrogen introduction channels. That is to say, that the yield of this type of cell is divided by a factor 2 to 3 compared to what one could hope for. This is believed to be due to the fact that the support layer 4 penetrates at least partially into the channels and that the catalyst layer 5 interacts with hydrogen only at the outlet of the channels 13.
  • An object of the present invention is to provide a new integrated fuel cell structure for improving the electrochemical efficiency per unit area.
  • Another object of the present invention is to provide a method of manufacturing such a fuel cell.
  • Another object of the present invention is to provide such a simple structure fuel cell.
  • the present invention provides a fuel cell cell whose active stack rests on a thin conductive layer, supported on a plate provided with transverse gas inlet channels, the thin conductive layer protruding into the active stack with respect to each channel and being transparent to said gas.
  • the thin conductive layer is a layer of gold.
  • the various active layers of the fuel cell follow the profile of the protuberances of the thin conductive layer.
  • the present invention also provides a method of manufacturing a fuel cell stack comprising the steps of providing a support plate; digging non-through channels from a first face of the support plate; coating said channels with a first material; forming a recess from the second face of the plate, this recess disengaging the ends of the first material; depositing on the second face a thin layer of a hydrogen-transparent conductive material; removing the first layer of material at least under the thin layer of a conductive material; and forming in said recess a stack of layers suitable for constituting a fuel cell whose lower face must receive hydrogen.
  • the materials of said stack of layers are deposited by an inkjet process.
  • FIGS. 2A to 2E are schematic sectional views illustrating successive steps of manufacturing a fuel cell cell according to the present invention.
  • a support plate To simplify the present description, it will be placed in the case where this support plate is silicon but the skilled person will understand that other types of materials can be used, which will lead to corresponding adaptations in the choice of associated methods, in particular etching processes, and the choice of insulation materials.
  • the Figure 2A represents a silicon wafer 21 coated on its upper and lower faces (or front and back) with protective layers 22 and 23.
  • the protective layer 23 on the side of the back face is etched to define openings therein. 25 channels are dug according to the contours defined by these openings, by an anisotropic etching process, commonly a plasma etching.
  • a material 26 is deposited in the channels 25 to coat their walls and bottoms, as shown, or to fill them completely. As will be seen below, this material must be selectively etchable with respect to silicon and a metal.
  • the coating 26 consists of a layer of silicon oxide obtained by thermal growth.
  • the protective layers 22 and 23 may also be made of silicon oxide, for example obtained by deposition.
  • an opening is defined in the upper protective layer 22 and a recess 28 is etched in the front face of the plate 21.
  • the recess 28 is deep enough to extend beyond the bottoms of the channels 25 covered by the diaper 26.
  • the etching is such that it does not attack the material of the layer 26 and that there therefore remain protrusions of the material of the layer 26 at the bottom of the recess 28.
  • these protuberances will have different shapes, depending on the shape of the bottoms of the channels resulting from the plasma etching, or other etching of realization of these channels.
  • These protuberances will have for example the shape of rounded domes.
  • a layer of a metal or alloy thick enough to be a good conductor of electricity and sufficiently thin to be transparent to hydrogen has been deposited on the upper face of the structure.
  • a gold layer having a thickness of the order of 500 nm may be chosen.
  • the material of the layer 26 is removed, at least at the bottom of the channels 25, where this layer is covered with the conductive layer 29. Protuberances 30 of the gold layer 29 are thus preserved.
  • the support plate 21, in the case where it is a silicon wafer may have a thickness of the order of 300 to 500 ⁇ m, that the channels 25 may be circular perforations with a diameter of the order of 40 to 50 microns, at a pitch of 40 to 50 microns and that the entire perforated zone may have a surface of the order of cm 2 .
  • the protuberances 30 of the gold layer 29 may have a height of 10 to 20 ⁇ m.
  • the support plate is designated by the reference 21, the channels by the reference 25, the thin conductive layer transparent to hydrogen by the reference 29, the first catalyst layer by the reference 5, the electrolyte layer. by the reference 6, the second catalyst layer by the reference 7, and the upper electrode perforated or transparent to oxygen by the reference 31.
  • the first catalyst layer 5 is deposited so as to have a substantially flat upper surface.
  • the electrolyte layer 6 is deposited so as to see a substantially constant thickness (deposition) and the second catalyst layer 7 is deposited to be present only in the central cuvette of the catalyst layer 6 resulting from the conformal deposition of the this.
  • An insulator 32 is formed at the locations where the first conductive layer 29 may be in contact with the second conductive layer 31.
  • the figure 4 represents a second embodiment of the present invention in which each of the deposits of the active layers 5, 6 and 7 is a compliant deposit.
  • the upper catalyst layer does not come into contact with the first electrode 29.
  • the figure 5 illustrates another embodiment of conformal deposition in which the upper metallization layer comes into contact with the edge of the recess 28 and could therefore be short-circuited with the lower electrode 29.
  • the insulating layer 32 is extended to extend on the side walls of the recess 28 in which are formed the active layers.
  • the deposits of the materials of the layers 5, 6 and 7 can be made by inkjet, the current technologies making it possible to obtain design definitions of the order of a few tens of ⁇ m, this which is compatible with the elementary dimensions of the cells according to the present invention in which, as previously indicated, the perforations have diameters of the order of fifty microns.
  • the variants illustrated in Figures 4 and 5 are intended to increase the contact area between the various active layers and between the catalyst layers and the arrival zones of hydrogen and oxygen, in order to increase the yields of the cells concerned.
  • the embodiments of the Figures 6 and 7 take over the structure of the figure 5 and add thereto a growth of nanotubes, for example carbon nanotubes on the upper and lower surfaces of the stack and in particular in the channels 25.
  • nanotubes for example carbon nanotubes on the upper and lower surfaces of the stack and in particular in the channels 25.
  • the provision of such lining by carbon nanotubes makes it possible to improve on the other hand, the management of the water within the structure due to the hydrophobic character of the nanotubes, on the other hand, the thermal management of the battery core due to the low thermal resistance of these nanotubes.
  • a recess has been formed on the underside of the wafer facing the perforated area.
  • this recess is intended to protect the carbon nanotubes. Note that such a recess can be provided in the other embodiments to allow to reduce the height of the hydrogen supply channels.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

The invention relates to a fuel cell whose active stack (5, 6, 7) is placed on a thin conductor layer (29) supported by a plate (21) which is provided with gas supply transversal channels (25), wherein said thin layer is projected into the active stack in front of each channel and is transparent to said gas.

Description

Domaine de l'inventionField of the invention

La présente invention concerne une pile à combustible et un procédé de fabrication de pile à combustible intégrée.The present invention relates to a fuel cell and an integrated fuel cell manufacturing method.

Exposé de l'art antérieurPresentation of the prior art

La figure 1 représente un exemple de cellule de pile à combustible intégrée réalisée en utilisant des techniques de microélectronique. Cette cellule est formée sur une plaque support constituée d'une plaquette de silicium 1 revêtue d'une première couche isolante 2 fine et d'une seconde couche isolante 3 plus épaisse. Une ouverture est formée dans une partie de la couche isolante 3. Dans cette ouverture sont successivement déposées une couche support 4, une couche de catalyseur 5, une couche d'électrolyte 6 et une seconde couche de catalyseur 7. L'ensemble de ces couches constitue un empilement actif 8. Une électrode 10, placée sur la première couche isolante 2, est en contact avec la couche support 4 du côté de la face inférieure de la cellule de pile. Une ouverture 11 dans la seconde couche isolante 3 permet d'accéder à l'électrode 10. Une électrode supérieure 12 est en contact avec la couche de catalyseur supérieure 7. Les électrodes 10 et 12 sont munies d'ouvertures, et des canaux 13 sont formés dans la plaquette de silicium 1 en regard des ouvertures dans la métallisation de face inférieure. Les électrodes inférieure 10 et supérieure 12 constituent respectivement un collecteur d'anode et un collecteur de cathode.The figure 1 represents an example of an integrated fuel cell cell made using microelectronics techniques. This cell is formed on a support plate consisting of a silicon wafer 1 coated with a first insulating thin layer 2 and a second insulating layer 3 thicker. An opening is formed in a portion of the insulating layer 3. In this opening are successively deposited a support layer 4, a catalyst layer 5, an electrolyte layer 6 and a second catalyst layer 7. All of these layers constitutes an active stack 8. An electrode 10, placed on the first insulating layer 2, is in contact with the support layer 4 on the side of the lower face of the cell stack. An opening 11 in the second insulating layer 3 provides access to the electrode 10. An upper electrode 12 is in contact with the upper catalyst layer 7. The electrodes 10 and 12 are provided with openings, and channels 13 are formed in the silicon wafer 1 facing openings in the lower face metallization. The lower and upper electrodes 12 respectively constitute an anode collector and a cathode collector.

L'électrolyte 6 est par exemple un acide polymère tel que du Nafion sous forme solide et les couches de catalyseur sont par exemple des couches à base de carbone et de platine. Ceci ne constitue qu'un exemple de réalisation. Divers types de piles à combustible réalisables sous la forme illustrée en figure 1 sont connus dans la technique.The electrolyte 6 is, for example, a polymeric acid such as Nafion in solid form and the catalyst layers are, for example, layers based on carbon and platinum. This is only an example of realization. Various types of fuel cells that can be produced in the form illustrated in figure 1 are known in the art.

Pour faire fonctionner la pile à combustible, on injecte de l'hydrogène selon la flèche H2 du côté de la face inférieure et de l'air (porteur d'oxygène) est injecté du côté de là face supérieure. L'hydrogène est "décomposé" au niveau de la couche de catalyseur 5 pour former d'une part des protons H+ qui se dirigent vers l'électrolyte 6 et d'autre part des électrons qui se dirigent, par l'extérieur de la pile, vers le collecteur d'anode 10. Les protons H+ traversent l'électrolyte 6 jusqu'à rejoindre la couche de catalyseur 7 où ils se recombinent avec l'oxygène et des électrons arrivant de l'extérieur de la pile par le collecteur de cathode. De façon connue, avec une telle structure, on obtient un potentiel positif sur le collecteur de cathode 12 (côté oxygène) et un potentiel négatif sur le collecteur d'anode 10 (côté hydrogène).To operate the fuel cell, hydrogen is injected according to the arrow H 2 on the side of the lower face and the air (oxygen carrier) is injected on the side of the upper face. The hydrogen is "decomposed" at the level of the catalyst layer 5 to form, on the one hand, H + protons which are directed towards the electrolyte 6 and, on the other hand, electrons which are directed by the outside of the stack, to the anode collector 10. The H + protons pass through the electrolyte 6 to join the catalyst layer 7 where they recombine with oxygen and electrons arriving from the outside of the cell by the collector cathode. In known manner, with such a structure, a positive potential is obtained on the cathode collector 12 (oxygen side) and a negative potential on the anode collector 10 (hydrogen side).

Un inconvénient de ce type de cellule de pile à combustible réside dans les phénomènes apparaissant au niveau du débouché des canaux 13 d'introduction d'hydrogène. Il s'avère en pratique qu'au lieu que les réactions se produisent sur toute la surface de la couche de catalyseur inférieure 5, ces réactions ne surviennent en fait que sur une partie de cette surface correspondant sensiblement à la surface occupée par les ouvertures des canaux d'introduction d'hydrogène. C'est-à-dire, que le rendement de ce type de pile est divisé par un facteur 2 à 3 par rapport à ce que l'on pourrait en espérer. On peut penser que ceci est dû au fait que la couche support 4 pénètre au moins partiellement dans les canaux et que la couche de catalyseur 5 n'interagit avec l'hydrogène qu'au niveau du débouché des canaux 13.A disadvantage of this type of fuel cell is the phenomena occurring at the outlet of the channels 13 for introducing hydrogen. It turns out in practice that instead of the reactions occurring over the entire surface of the lower catalyst layer 5, these reactions actually occur only on a part of this surface corresponding substantially to the area occupied by the openings of the hydrogen introduction channels. That is to say, that the yield of this type of cell is divided by a factor 2 to 3 compared to what one could hope for. This is believed to be due to the fact that the support layer 4 penetrates at least partially into the channels and that the catalyst layer 5 interacts with hydrogen only at the outlet of the channels 13.

Résumé de l'inventionSummary of the invention

Un objet de la présente invention est de prévoir une nouvelle structure de pile à combustible intégrée permettant d'améliorer le rendement électrochimique par unité de surface.An object of the present invention is to provide a new integrated fuel cell structure for improving the electrochemical efficiency per unit area.

Un autre objet de la présente invention est de prévoir un procédé de fabrication d'une telle pile à combustible.Another object of the present invention is to provide a method of manufacturing such a fuel cell.

Un autre objet de la présente invention est de prévoir une telle pile à combustible de structure simple.Another object of the present invention is to provide such a simple structure fuel cell.

Pour atteindre ces objets, la présente invention prévoit une cellule de pile à combustible dont l'empilement actif repose sur une couche conductrice mince, s'appuyant sur une plaque munie de canaux transversaux d'arrivée de gaz, la couche conductrice mince faisant saillie dans l'empilement actif au regard de chaque canal et étant transparente audit gaz.To achieve these objects, the present invention provides a fuel cell cell whose active stack rests on a thin conductive layer, supported on a plate provided with transverse gas inlet channels, the thin conductive layer protruding into the active stack with respect to each channel and being transparent to said gas.

Selon un mode de réalisation de la présente invention, la couche conductrice mince est une couche d'or.According to one embodiment of the present invention, the thin conductive layer is a layer of gold.

Selon un mode de réalisation de la présente invention, les diverses couches actives de la pile à combustible épousent le profil des protubérances de la couche conductrice mince.According to one embodiment of the present invention, the various active layers of the fuel cell follow the profile of the protuberances of the thin conductive layer.

La présente invention prévoit aussi un procédé de fabrication d'une pile de cellule à combustible comprenant les étapes consistant à prévoir une plaque support ; creuser des canaux non débouchants à partir d'une première face de la plaque support ; revêtir lesdits canaux d'un premier matériau ; former un évidement à partir de la deuxième face de la plaque, cet évidement dégageant les extrémités du premier matériau ; déposer sur la deuxième face une couche mince d'un matériau conducteur transparent à l'hydrogène ; éliminer la première couche de matériau au moins sous la couche mince d'un matériau conducteur ; et former dans ledit évidement un empilement de couches propre à constituer une pile à combustible dont la face inférieure doit recevoir de l'hydrogène.The present invention also provides a method of manufacturing a fuel cell stack comprising the steps of providing a support plate; digging non-through channels from a first face of the support plate; coating said channels with a first material; forming a recess from the second face of the plate, this recess disengaging the ends of the first material; depositing on the second face a thin layer of a hydrogen-transparent conductive material; removing the first layer of material at least under the thin layer of a conductive material; and forming in said recess a stack of layers suitable for constituting a fuel cell whose lower face must receive hydrogen.

Selon un mode de réalisation de la présente invention, les matériaux dudit empilement de couches sont déposés par un procédé de jet d'encre.According to one embodiment of the present invention, the materials of said stack of layers are deposited by an inkjet process.

Brève description des dessinsBrief description of the drawings

Ces objets, caractéristiques et avantages, ainsi que d'autres de la présente invention seront exposés en détail dans la description suivante de modes de réalisation particuliers faite à titre non-limitatif en relation avec les figures jointes parmi lesquelles :

  • la figure 1 est une vue en coupe d'une cellule de pile à combustible connue ; et
  • les figures 2A à 2E sont des vues en coupe illustrant des étapes successives de fabrication d'une pile à combustible selon la présente invention ; et
  • les figures 3 à 7 illustrent des modes de réalisation de la présente invention:
These and other objects, features, and advantages of the present invention will be set forth in detail in the following description of particular embodiments given as a non-limiting example in connection with the accompanying drawings in which:
  • the figure 1 is a sectional view of a known fuel cell cell; and
  • the Figures 2A to 2E are sectional views illustrating successive steps of manufacturing a fuel cell according to the present invention; and
  • the Figures 3 to 7 illustrate embodiments of the present invention:

Par souci de clarté, comme cela est habituel dans la représentation des microcomposants, les éléments des diverses vues en coupe et en perspective ne sont pas tracés à l'échelle.For the sake of clarity, as is usual in the representation of microcomponents, the elements of the various sectional and perspective views are not drawn to scale.

Description détailléedetailed description

Les figures 2A à 2E sont des vues en coupe schématiques illustrant des étapes successives de fabrication d'une cellule de pile à combustible selon la présente invention. Pour cette fabrication, on part d'une plaque support. Pour simplifier la présente description, on se placera dans le cas où cette plaque support est en silicium mais l'homme du métier comprendra que d'autres types de matériaux peuvent être utilisés, ce qui entraînera des adaptations correspondantes dans le choix des procédés associés, notamment des procédés de gravure, et le choix des matériaux d'isolement.The Figures 2A to 2E are schematic sectional views illustrating successive steps of manufacturing a fuel cell cell according to the present invention. For this production, we start from a support plate. To simplify the present description, it will be placed in the case where this support plate is silicon but the skilled person will understand that other types of materials can be used, which will lead to corresponding adaptations in the choice of associated methods, in particular etching processes, and the choice of insulation materials.

Ainsi, la figure 2A représente une plaque de silicium 21 revêtue sur ses faces supérieure et inférieure (ou avant et arrière) de couches de protection 22 et 23. La couche de protection 23 du côté de la face arrière est gravée pour y définir des ouvertures. Des canaux 25 sont creusés selon les contours définis par ces ouvertures, par un procédé de gravure anisotrope, couramment une gravure plasma.So, the Figure 2A represents a silicon wafer 21 coated on its upper and lower faces (or front and back) with protective layers 22 and 23. The protective layer 23 on the side of the back face is etched to define openings therein. 25 channels are dug according to the contours defined by these openings, by an anisotropic etching process, commonly a plasma etching.

A l'étape suivante illustrée en figure 2B, un matériau 26 est déposé dans les canaux 25 pour revêtir leurs parois et leurs fonds, comme cela est représenté, ou pour les remplir complètement. Comme on le verra ci-après, ce matériau doit être gravable sélectivement par rapport au silicium et à un métal. Dans un exemple d'application de la présente invention, le revêtement 26 est constitué d'une couche d'oxyde de silicium obtenue par croissance thermique. Les couches de protection 22 et 23 pourront également être en oxyde de silicium, par exemple obtenues par dépôt.At the next step illustrated in Figure 2B a material 26 is deposited in the channels 25 to coat their walls and bottoms, as shown, or to fill them completely. As will be seen below, this material must be selectively etchable with respect to silicon and a metal. In an exemplary application of the present invention, the coating 26 consists of a layer of silicon oxide obtained by thermal growth. The protective layers 22 and 23 may also be made of silicon oxide, for example obtained by deposition.

A l'étape illustrée en figure 2C, on définit une ouverture dans la couche de protection supérieure 22 et on grave dans la face avant de la plaque 21 un évidement 28. L'évidement 28 est suffisamment profond pour s'étendre au-delà des fonds des canaux 25 recouverts de la couche 26. La gravure est telle qu'elle n'attaque pas le matériau de la couche 26 et qu'il reste donc des protubérances du matériau de la couche 26 au fond de l'évidement 28. Selon le mode de fabrication, ces protubérances auront des formes différentes, selon la forme des fonds des canaux résultant de la gravure plasma, ou autre gravure de réalisation de ces canaux. Ces protubérances auront par exemple la forme de dômes arrondis.At the step illustrated in Figure 2C an opening is defined in the upper protective layer 22 and a recess 28 is etched in the front face of the plate 21. The recess 28 is deep enough to extend beyond the bottoms of the channels 25 covered by the diaper 26. The etching is such that it does not attack the material of the layer 26 and that there therefore remain protrusions of the material of the layer 26 at the bottom of the recess 28. According to the method of manufacture, these protuberances will have different shapes, depending on the shape of the bottoms of the channels resulting from the plasma etching, or other etching of realization of these channels. These protuberances will have for example the shape of rounded domes.

A l'étape illustrée en figure 2D, on a déposé sur la face supérieure de la structure une couche d'un métal ou d'un alliage suffisamment épais pour être un bon conducteur de l'électricité et suffisamment fin pour être transparent à l'hydrogène. On pourra par exemple choisir une couche d'or d'une épaisseur de l'ordre de 500 nm.At the step illustrated in 2D figure a layer of a metal or alloy thick enough to be a good conductor of electricity and sufficiently thin to be transparent to hydrogen has been deposited on the upper face of the structure. For example, a gold layer having a thickness of the order of 500 nm may be chosen.

Ensuite, à l'étape illustrée à la figure 2E, on élimine le matériau de la couche 26, au moins au fond des canaux 25, là où cette couche est recouverte de la couche conductrice 29. On conserve donc des protubérances 30 de la couche d'or 29.Then, at the step illustrated in figure 2E the material of the layer 26 is removed, at least at the bottom of the channels 25, where this layer is covered with the conductive layer 29. Protuberances 30 of the gold layer 29 are thus preserved.

A titre d'exemple d'ordre de grandeur, on notera que la plaque support 21, dans le cas où il s'agit d'une plaque de silicium peut avoir une épaisseur de l'ordre de 300 à 500 µm, que les canaux 25 peuvent être des perforations circulaires d'un diamètre de l'ordre de 40 à 50 µm, à un pas de 40 à 50 µm et que l'ensemble de la zone perforée peut avoir une surface de l'ordre du cm2. Les protubérances 30 de la couche d'or 29 peuvent avoir une hauteur de 10 à 20 µm.By way of example of an order of magnitude, it will be noted that the support plate 21, in the case where it is a silicon wafer, may have a thickness of the order of 300 to 500 μm, that the channels 25 may be circular perforations with a diameter of the order of 40 to 50 microns, at a pitch of 40 to 50 microns and that the entire perforated zone may have a surface of the order of cm 2 . The protuberances 30 of the gold layer 29 may have a height of 10 to 20 μm.

A partir de la structure obtenue en figure 2E, on peut procéder au dépôt de l'empilement actif 8 décrit en relation avec la figure 1, étant entendu que, dans cet empilement actif, la couche support 4 devient inutile. En effet, cette couche support avait pour but d'éviter que le matériau de la première couche de catalyseur 5 redescende dans les canaux. La forme en relief, éventuellement bombée, des protubérances d'or 30 entraîne que l'hydrogène quitte les canaux 23 vers le haut et vers les côtés et se disperse mieux dans la couche de catalyseur inférieure.From the structure obtained in figure 2E it is possible to deposit the active stack 8 described in connection with the figure 1 , it being understood that in this active stack, the support layer 4 becomes useless. Indeed, this support layer was intended to prevent the material of the first catalyst layer 5 back down into the channels. The raised, possibly domed, shape of the gold protuberances causes the hydrogen to leave the channels 23 up and to the sides and disperse better in the lower catalyst layer.

Diverses façons de réaliser l'empilement actif 8 vont être décrites en relation avec les figures 3 à 7. Dans ces figures, la plaque support est désignée par la référence 21, les canaux par la référence 25, la couche conductrice mince transparente à l'hydrogène par la référence 29, la première couche de catalyseur par la référence 5, la couche d'électrolyte par la référence 6, la seconde couche de catalyseur par la référence 7, et l'électrode supérieure perforée ou transparente à l'oxygène par la référence 31.Various ways of carrying out the active stacking 8 will be described in relation to the Figures 3 to 7 . In these figures, the support plate is designated by the reference 21, the channels by the reference 25, the thin conductive layer transparent to hydrogen by the reference 29, the first catalyst layer by the reference 5, the electrolyte layer. by the reference 6, the second catalyst layer by the reference 7, and the upper electrode perforated or transparent to oxygen by the reference 31.

Dans le mode de réalisation de la figure 3, la première couche de catalyseur 5 est déposée de façon à avoir une surface supérieure sensiblement plane. La couche d'électrolyte 6 est déposée de façon à voir une épaisseur sensiblement constante (dépôt conforme) et la deuxième couche de catalyseur 7 est déposée pour être présente seulement dans la cuvette centrale de la couche de catalyseur 6 résultant du dépôt conforme de celle-ci. Un isolant 32 est formé aux emplacements où la première couche conductrice 29 risque d'être en contact avec la deuxième couche conductrice 31.In the embodiment of the figure 3 the first catalyst layer 5 is deposited so as to have a substantially flat upper surface. The electrolyte layer 6 is deposited so as to see a substantially constant thickness (deposition) and the second catalyst layer 7 is deposited to be present only in the central cuvette of the catalyst layer 6 resulting from the conformal deposition of the this. An insulator 32 is formed at the locations where the first conductive layer 29 may be in contact with the second conductive layer 31.

La figure 4 représente un deuxième mode de réalisation de la présente invention dans lequel chacun des dépôts des couches actives 5, 6 et 7 est un dépôt conforme. Dans ce mode de réalisation la couche de catalyseur supérieure ne vient pas en contact avec la première électrode 29.The figure 4 represents a second embodiment of the present invention in which each of the deposits of the active layers 5, 6 and 7 is a compliant deposit. In this embodiment, the upper catalyst layer does not come into contact with the first electrode 29.

La figure 5 illustre un autre mode de réalisation de dépôt conforme dans lequel la couche de métallisation supérieure vient en contact avec le bord de l'évidement 28 et risquerait donc d'être en court-circuit avec l'électrode inférieure 29. Pour éviter ce risque de court-circuit, la couche isolante 32 est prolongée pour s'étendre sur les parois latérales de l'évidement 28 dans lequel sont formées les couches actives.The figure 5 illustrates another embodiment of conformal deposition in which the upper metallization layer comes into contact with the edge of the recess 28 and could therefore be short-circuited with the lower electrode 29. To avoid this risk of short -circuit, the insulating layer 32 is extended to extend on the side walls of the recess 28 in which are formed the active layers.

Selon un aspect de l'invention, les dépôts des matériaux des couches 5, 6 et 7 peuvent être réalisés par jet d'encre, les technologies actuelles permettant d'obtenir des définitions de motif de l'ordre de quelques dizaines de µm, ce qui est compatible avec les dimensions élémentaires des cellules selon la présente invention dans lesquelles, comme on l'a indiqué précédemment, les perforations ont des diamètres de l'ordre de la cinquantaine de µm.According to one aspect of the invention, the deposits of the materials of the layers 5, 6 and 7 can be made by inkjet, the current technologies making it possible to obtain design definitions of the order of a few tens of μm, this which is compatible with the elementary dimensions of the cells according to the present invention in which, as previously indicated, the perforations have diameters of the order of fifty microns.

Les variantes illustrées en figures 4 et 5 sont destinées à augmenter la surface de contact entre les diverses couches actives et entre les couches de catalyseur et les zones d'arrivée d'hydrogène et d'oxygène, afin d'augmenter les rendements des piles concernées.The variants illustrated in Figures 4 and 5 are intended to increase the contact area between the various active layers and between the catalyst layers and the arrival zones of hydrogen and oxygen, in order to increase the yields of the cells concerned.

Les modes de réalisation des figures 6 et 7 reprennent la structure de la figure 5 et y ajoutent une croissance de nanotubes, par exemple de nanotubes de carbone sur les surfaces supérieure et inférieure de la pile et notamment dans les canaux 25. La prévision d'un tel tapissage par des nanotubes de carbone permet d'améliorer, d'une part, la gestion de l'eau au sein de la structure en raison du caractère hydrophobe des nanotubes, d'autre part, la gestion thermique du coeur de pile en raison de la faible résistance thermique de ces nanotubes.The embodiments of the Figures 6 and 7 take over the structure of the figure 5 and add thereto a growth of nanotubes, for example carbon nanotubes on the upper and lower surfaces of the stack and in particular in the channels 25. The provision of such lining by carbon nanotubes makes it possible to improve on the other hand, the management of the water within the structure due to the hydrophobic character of the nanotubes, on the other hand, the thermal management of the battery core due to the low thermal resistance of these nanotubes.

Dans le mode de réalisation de la figure 7, on a formé un évidement sur la face inférieure de la plaquette en regard de la zone perforée. Dans ce mode de réalisation, cet évidement est destiné à protéger les nanotubes de carbone. On notera qu'un tel évidement peut être prévu dans les autres modes de réalisation pour permettre de réduire la hauteur des canaux d'amenée d'hydrogène.In the embodiment of the figure 7 a recess has been formed on the underside of the wafer facing the perforated area. In this embodiment, this recess is intended to protect the carbon nanotubes. Note that such a recess can be provided in the other embodiments to allow to reduce the height of the hydrogen supply channels.

Claims (5)

  1. A fuel cell having its active stack (8) resting on a thin conductive layer (29), bearing on a wafer (21) provided with through gas inlet channels (25), the thin conductive layer protruding in the active stack in front of each channel and being transparent to said gas.
  2. The fuel cell of claim 1, wherein the thin conductive layer is a gold layer.
  3. The fuel cell of claim 1, wherein the various active layers of the fuel cell conform to the profile of the protrusions (30) of the thin conductive layer.
  4. A method for manufacturing a fuel cell, comprising the steps of:
    providing a support wafer (21);
    digging non-through channels (25) from a first surface of the support wafer (21);
    coating said channels with a first material (26);
    forming a recess (28) from the second surface of the wafer, this recess exposing the ends of the first material;
    depositing on the second surface a thin layer of a conductive material (29) transparent to hydrogen;
    eliminating the first layer of the material (26) at least under the thin layer of a conductive material; and
    forming in said recess a stack of layers (8) capable of forming a fuel cell having a lower surface that can receive hydrogen.
  5. The method of claim 4, wherein the materials of said stacking of layers are deposited by an inkjet method.
EP06847219A 2005-12-27 2006-12-27 Integrated fuel cell and a production method Expired - Fee Related EP1982380B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0554104A FR2895573A1 (en) 2005-12-27 2005-12-27 Fuel cell for silicon support plate has catalyst and electrolyte layers placed on transparent thin conductor layer supported by support plate which is provided with gas supply transversal channels, where conductor layer is gold layer
PCT/FR2006/051430 WO2007074317A1 (en) 2005-12-27 2006-12-27 Integrated fuel cell and a production method

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EP1982380A1 EP1982380A1 (en) 2008-10-22
EP1982380B1 true EP1982380B1 (en) 2010-05-12

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SG2012070850A (en) * 2007-10-01 2014-04-28 Kovio Inc Profile engineered thin film devices and structures
EP2211406B1 (en) * 2009-01-15 2012-05-30 STMicroelectronics (Tours) SAS Fuel cell electrode
WO2010092281A1 (en) * 2009-02-11 2010-08-19 Stmicroelectronics (Tours) Sas Fuel cell with cathode water removal
IT201800004765A1 (en) * 2018-04-20 2019-10-20 PROTECTION OF A METALLIC SUBSTRATE FOR SOLID OXIDE CELL STACKS BY INKJET PRINTING

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US20030096146A1 (en) * 2001-03-30 2003-05-22 Foster Ronald B. Planar substrate-based fuel cell Membrane Electrode Assembly and integrated circuitry
EP1258937A1 (en) * 2001-05-17 2002-11-20 STMicroelectronics S.r.l. Micro silicon fuel cell, method of fabrication and self-powered semiconductor device integrating a micro fuel cell
US6869711B2 (en) * 2001-09-10 2005-03-22 Industrial Technology Research Institute Highly efficient electrochemical reaction device
WO2004091026A2 (en) * 2003-04-04 2004-10-21 Sagem Sa Micro fuel cell, particularly for use with portable electronic devices and telecommunication devices
FR2857163B1 (en) * 2003-07-01 2008-12-26 Commissariat Energie Atomique FUEL CELL IN WHICH A FLUID CIRCULARLY CIRCUMSTANCES PARALLEL TO THE ELECTROLYTIC MEMBRANE AND METHOD OF MANUFACTURING SUCH A FUEL CELL
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CN101361217A (en) 2009-02-04
US20090311572A1 (en) 2009-12-17
WO2007074317A1 (en) 2007-07-05
FR2895573A1 (en) 2007-06-29
DE602006014307D1 (en) 2010-06-24
EP1982380A1 (en) 2008-10-22

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